Herbicidal mixtures

ABSTRACT

The present invention provides a composition comprising (A) a compound of formula (I):wherein R1 is methyl or methoxy, R2 is hydrogen, methyl or ethoxy and A is a substituted heteroaryl group, or an N-oxide or salt form thereof, and (B) one or more further herbicides; as well as the use of such compositions in controlling plants or inhibiting plant growth.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to Patent Application No. GB1901559.3filed in the United Kingdom on Feb. 5, 2019, the entire contents of allof which are incorporated herein by reference.

The present invention relates novel herbicidal compositions and theiruse in controlling plants or inhibiting plant growth.

Herbicidal dihydro-hydantoins of the formula

wherein A is a pyridine ring are taught in U.S. Pat. No. 4,600,430.Further hydantoins wherein A is an isoxazole ring are taught in e.g.U.S. Pat. No. 4,302,239 and Canadian Patent No. 1205077.

WO 2015/052076 discloses the compounds 1.1

1.2

and 1.3

and their use as herbicides, whilst compound 1.4

is described in WO2015/059262, compound 1.5

is described in WO 2015/097043 and compound 1.6

is described in WO 2015/193202. WO 2018/065311 describes mixtures ofthese compounds with certain herbicidal pyrrolidonone derivatives.

The object of the present invention is to provide herbicidal mixtureswhich are highly effective against various weed species at low doseand/or have increased crop tolerance.

The present invention is based on the finding that novelpyrazole-pyrrolidine carboxamides of formula (II) as defined herein areparticularly efficacious as herbicides. They are thus particularlysuitable as mixture partners for herbicidal dihydro-hydantoins. This inone aspect, the present invention provides a composition comprising (A)a compound of formula (I):

wherein R¹ is methyl or methoxy, R² is hydrogen, methyl or ethoxy and Ais a substituted heteroaryl group and wherein said compound is selectedfrom the group consisting of:

or an N-oxide or salt form thereof, and,(B) one or more compounds of formula (II)

wherein; R^(B1) is H, methyl, or methoxy; X is O or S; Q¹ is a di- ortri-substituted pyrazole, substituted on one ring nitrogen by R^(B2) andsubstituted on at least one ring carbon by R^(B3) wherein R^(B2) isC₁-C₃ alkyl or C₁-C₃fluoroalkyl and each R^(B3) is independentlyhalogen, C₁-C₃fluoroalkyl, C₁-C₃haloalkoxy, C₁-C₃alkoxy, orC₁-C₃haloalkyl, C₁-C₃fluoroalkyl, C₁-C₃haloalkoxy, C₁-C₃alkoxy, orC₁-C₃alkyl; or Q¹ is a di-substituted pyrazole, substituted on one ringnitrogen by R^(B2) and on an adjacent ring carbon by R^(B3), whereinR^(B2) is C₁-C₃ alkyl and R^(B3) is C₁-C₃fluoroalkyl or or C₁-C₃alkyland R^(B2) and R^(B3) together with the atoms to which they are joinedand Q¹ form an eight or nine-membered fused heterocyclic bicyclic ringsystem; Q² is a phenyl, pyridinyl, or thienyl ring system, optionallysubstituted by 1, 2, or 3 R^(B5) substituents; and each R^(B5) isindependently halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, cyano, nitro, C₁-C₆alkylthio, C₁-C₆alkylsulphinyl, orC₁-C₆alkylsulphonyl; or an N-oxide, or a salt form thereof.

In a second aspect, the invention provides the use of a composition ofthe invention as a herbicide.

In a third aspect, the invention provides a method of controllingplants, comprising applying to the plants or to the locus of the plants,a herbicidally effective amount of a composition of the invention.

In a fourth aspect, the invention provides a method of inhibiting plantgrowth, comprising applying to the plants or to the locus thereof, aherbicidally effective amount of a composition of the invention.

In a fifth aspect, the invention provides a method of controlling weedsin crops of useful plants, comprising applying to the weeds or to thelocus of the weeds, or to the useful plants or to the locus of theuseful plants, a herbicidally effective amount of a composition of theinvention.

In a sixth aspect, the invention provides a method of selectivelycontrolling grasses and/or weeds in crops of useful plants whichcomprises applying to the useful plants or locus thereof or to the areaof cultivation a herbicidally effective amount of a composition of theinvention.

When active ingredients are combined, the activity to be expected (E)for any given active ingredient combination obeys the so-called ColbyFormula and can be calculated as follows (Colby, S. R., Calculatingsynergistic and antagonistic responses of herbicide combination, Weeds,Vol. 15, pages 20-22; 1967):

ppm=milligrams of active ingredient (a. i.) per liter

X=% action by first active ingredient using p ppm of the activeingredient

Y=% action by second active ingredient sing q ppm of the activeingredient.

According to Colby, the expected action of active ingredients A+B usingp+q ppm of active ingredient is represented by the following formula:

$E = {X + Y - \frac{X \cdot Y}{100}}$

If the action actually observed (0) is greater than the expected actionE then the action of the combination is super-additive, i.e. there is asynergistic effect. In mathematical terms, synergism corresponds to apositive value for the difference of (O-E). In the case of purelycomplementary addition of activities (expected activity), saiddifference (O-E) is zero. A negative value of said difference (O-E)signals a loss of activity compared to the expected activity.

Compounds of formula (I) and formula (II) are both effective herbicidalcompounds, as shown in WO 2015/052076, WO2015/059262 WO 2015/097043 andWO 2015/193202 with respect to compounds of formula (I) and as shownherein with respect to compounds of formula (II). Accordingly, thecombination of the present invention takes advantage of their additiveactivity, and certain embodiments may exhibit a synergistic effect. Thisoccurs whenever the action of an active ingredient combination isgreater than the sum of the actions of the individual components.

Furthermore, besides any actual synergistic action with respect toherbicidal activity, the composition according to the invention may alsoexhibit further surprising advantageous properties. Examples of suchadvantageous properties include improved characteristics of the usefulplants including: emergence, crop yields, more developed root system,tillering increase, increase in plant height, bigger leaf blade, lessdead basal leaves, stronger tillers, greener leaf colour, lessfertilizers needed, less seeds needed, more productive tillers, earlierflowering, early grain maturity, less plant verse (lodging), increasedshoot growth, improved plant vigor, and early germination.

In addition, it is also possible that the composition of the inventionmay show increased crop tolerance, when compared with the effect of thecompound A (or B) alone. This occurs when the action of an activeingredient combination is less damaging to a useful crop than the actionof one of the active ingredients alone.

As used herein, the term “halogen” or “halo” refers to fluorine(fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo),preferably fluorine, chlorine or bromine.

As used herein, cyano means a —CN group.

As used herein, hydroxy means an —OH group.

As used herein, nitro means an —NO₂ group.

Each alkyl moiety either alone or as part of a larger group (such asalkoxy, alkylthio, haloalkyl, haloalkoxy et al.) may be straight-chainedor branched, and as used herein the term specifically also includescyclopropyl. Typically, the alkyl is, for example, methyl, ethyl,n-propyl, cylcopropyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, n-pentyl, neopentyl, or n-hexyl. The alkyl groups aregenerally C₁-C₆alkyl groups (except where already defined morenarrowly), but are preferably C₁-C₄alkyl or C₁-C₃alkyl groups, and, morepreferably, are C₁ or C₂alkyl groups (i.e. methyl or ethyl).

As used herein, the term “C₁-C₃alkoxy” refers to a radical of theformula —OR_(a) where R_(a) is a C₁-C₃alkyl radical as generally definedabove. Examples of C₁-C₃ alkoxy thus include methoxy, ethoxy, propoxy,and iso-propoxy.

As used herein, the term “C₁-C₃haloalkyl” refers to a C₁-C₃alkyl radicalas generally defined above substituted by one or more of the same ordifferent halogen atoms. Examples of C₁-C₃haloalkyl thus include,fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl,2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl,2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl.

As used herein, the term “C₁-C₃haloalkoxy” refers to a C₁-C₃alkoxy groupas defined above substituted by one or more of the same or differenthalogen atoms. Examples of C₁-C₃haloalkoxy thus include, fluoromethoxy,difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy,1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy,2,2-difluoroethoxy and 2,2,2-trichloroethoxy.

The term “C₁-C₆alkylthio” refers to the group C₁-C₆alkyl-S—, and is, forexample, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio,isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio orethylthio.

The term “C₁-C₆alkylsulfinyl” refers to the group C₁-C₆alkyl-S(O)—, andis, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl,isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinylor tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

The term “C₁-C₆alkylsulfonyl” refers to the group C₁-C₆alkyl-S(O)₂—, andis, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl,isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonylor tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

The compounds of formula (I) may exist as different geometric isomers,or in different tautomeric forms. This invention covers the use of allsuch isomers and tautomers, and mixtures thereof in all proportions, aswell as isotopic forms such as deuterated compounds. They may containone or more asymmetric centers and may thus give rise to optical isomersand diastereomers. While shown for formula (I) without respect tostereochemistry, the present invention includes the use of all suchoptical isomers and diastereomers as well as the racemic and resolved,enantiomerically pure R and S stereoisomers and other mixtures of the Rand S stereoisomers and agrochemically acceptable salts thereof. It isrecognized certain optical isomers or diastereomers may have favorableproperties over the other. Thus when disclosing and claiming theinvention, when a racemic mixture is disclosed, it is clearlycontemplated that both optical isomers, including diastereomers,substantially free of the other, are disclosed and claimed as well.

In particular, the present invention covers the following forms ofcompounds 1.1 to 1.6:

Similarly, presence of one or more possible asymmetric carbon atoms in acompound of formula (II) means that the compounds may occur in chiralisomeric forms, i.e., enantiomeric or diastereomeric forms. Alsoatropisomers may occur as a result of restricted rotation about a singlebond. Formula (II) is intended to include all those possible isomericforms and mixtures thereof. The present invention includes the use ofall those possible isomeric forms and mixtures thereof for a compound offormula (II). Likewise, formula (II) is intended to include all possibletautomers (including lactam-lactim tautomerism and keto-enoltautomerism) where present. The present invention thus includes the useof all possible tautomeric forms for a compound of formula (II).

Suitable salts include those derived from alkali or alkaline earthmetals and those derived from ammonia and amines. Preferred cationsinclude sodium, potassium, magnesium, and ammonium cations of theformula N⁺(R¹⁹R²⁰R²¹R²²) wherein R¹⁹, R²⁰, R²¹ and R²² are independentlyselected from hydrogen, C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl. Salts of thecompounds of formula (I) can be prepared by treatment of compounds offormula (I) with a metal hydroxide, such as sodium hydroxide, or anamine, such as ammonia, trimethylamine, diethanolamine,2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine,cyclododecylamine, or benzylamine. Amine salts are often preferred formsof the compounds of formula (I) because they are water-soluble and lendthemselves to the preparation of desirable aqueous based herbicidalcompositions.

Acceptable salts can be formed from organic and inorganic acids, forexample, acetic, propionic, lactic, citric, tartaric, succinic, fumaric,maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic,phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic,benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly knownacceptable acids when a compound of this invention contains a basicmoiety.

Throughout this document the expression “composition” stands for thevarious mixtures or combinations of components (A) and (B), for examplein a single “ready-mix” form, in a combined spray mixture composed fromseparate formulations of the single active ingredient components, suchas a “tank-mix”, and in a combined use of the single active ingredientswhen applied in a sequential manner, i.e. one after the other with areasonably short period, such as a few hours or days. The order ofapplying the components (A) and (B) is not essential for working thepresent invention.

The term “herbicide” as used herein means a compound that controls ormodifies the growth of plants. The term “herbicidally effective amount”means the quantity of such a compound or combination of such compoundsthat is capable of producing a controlling or modifying effect on thegrowth of plants. Controlling or modifying effects include all deviationfrom natural development, for example killing, retardation, leaf burn,albinism, dwarfing and the like.

The term “locus” as used herein means fields in or on which plants aregrowing, or where seeds of cultivated plants are sown, or where seedwill be placed into the soil. It includes soil, seeds, and seedlings, aswell as established vegetation.

The term “plants” refers to all physical parts of a plant, includingseeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, andfruits.

The term “plant propagation material” denotes all generative parts of aplant, for example seeds or vegetative parts of plants such as cuttingsand tubers. It includes seeds in the strict sense, as well as roots,fruits, tubers, bulbs, rhizomes, and parts of plants.

The term “safener” as used herein means a chemical that when used incombination with a herbicide reduces the undesirable effects of theherbicide on non-target organisms, for example, a safener protects cropsfrom injury by herbicides but does not prevent the herbicide fromkilling the weeds.

Preferred embodiments of the invention are as set out below.

In one embodiment, (A) is compound 1.1.

In one embodiment (A) is compound 1.2.

In one embodiment (A) is compound 1.3.

In one embodiment (A) is compound 1.4.

In one embodiment (A) is compound 1.5.

In one embodiment (A) is compound 1.6.

Compounds of formula (I) as described herein may be prepared bytechniques known to the person skilled in the art of organic chemistry.Methods for the production of compounds of formula (I) are described inWO2015/052076, WO2015/059262, WO2015/097043 and WO2015/193202.

With respect to compounds of formula (II), the preferred substituentsare as follows, and the skilled man will appreciate that for any one ofthese substituents and/or integers, any of the definitions given belowmay be combined with that of any other substituent and/or integer givenbelow or elsewhere in this document with respect to a compound offormula (II).

R^(B1) is preferably hydrogen or methyl.

Where X is S, compounds of formula (II) may be procidal, although theymay also retain a degree of intrinsic herbicidal activity and thus findutility in mixtures of the invention. However, it is particularlypreferred that compounds of formula (II) will have oxygen as substituentX.

As stated above, Q² is a phenyl, pyridinyl, or thienyl ring system,optionally substituted by 1, 2, or 3 R^(B5) substituents, and thus maybe represented by the following generic structure

wherein ring Q² is a phenyl, pyridinyl, or thienyl ring, n is an integeror 0, 1, 2, or 3, and the jagged line represents the point of attachmentof the ring to the rest of the molecule, in this case via the amidenitrogen. Preferably Q² is selected from the group consisting of Q²-1,Q²-2, Q²-3, Q²-4, Q²-5, and Q²-6, wherein R^(B5), n and the jagged lineare as described previously.

Also as defined herein, each R^(B5) is independently halogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, cyano, nitro,C₁-C₆alkylthio, C₁-C₆alkylsulphinyl, or C₁-C₆alkylsulphonyl. Preferablyn is 0, 1, or 2 and each R^(B5) is borne by a ring carbon atom. Morepreferably each R^(B5) is independently halogen, C₁-C₄ alkyl, C₁-C₀₃haloalkyl, C₁-C₃alkoxy, or C₁-C₃haloalkoxy; more preferably chloro,fluoro, bromo, C₁-C₂haloalkyl, C₁-C₂haloalkoxy, or C₁-C₂alkoxy; morepreferably still fluoro, ethyl, trifluoromethyl, difluoroethyl, methoxy,difluoromethoxy, or trifluoromethoxy. More preferably still, the valueof n is 1, 2 or 3. Particularly preferred are compounds of formula (II)wherein n is 2 and at least one R^(B5) is fluoro.

One of the key features of the compounds of formula (II) is that Q¹ is apyrazole moiety carrying at least two substituents, wherein one of saidsubstituents (R^(B2)) is borne by a ring nitrogen, and a secondsubstituent (R^(B3)) is borne on a ring carbon atom. Clearly with such aconfiguration, Q¹ is carbon linked to the rest of the molecule.

When Q¹ is di-substituted and R^(B3) is borne on the ring carbon atomadjacent the substituted ring nitrogen atom said R^(B3) substitutent maybe defined as R^(B3SN). For the avoidance of doubt R^(B3SN) is asub-definition of R^(B3) used purely to denote positional placementwithin the pyrazole moiety, and therefore R^(B3SN) is also selected fromthe group consisting of halogen, C₁-C₃fluoroalkyl, C₁-C₃haloalkoxy,C₁-C₃alkoxy, and C₁-C₃alkyl. Thus when Q¹ is disubstituted, it may berepresented by groups Q¹-2a, Q¹-2b, Q¹-2c, Q¹-2d, or Q1-e, as shownbelow, wherein R^(B2), R^(B3) and R^(B3SN) are as defined above and thejagged line denotes the point of attachment to the rest of the molecule,in this case through the carbon atom at the 4-position of thepyrrolidine ring,

with groups Q¹-2a and Q¹-2b being particularly preferred, and Q¹-2bbeing the most preferred of the di-substituted pyrazoles.

Where Q¹ is tri-substituted it may be represented by groups Q¹-3a orQ¹-3b, wherein the third substituent (R^(B3)) is also borne on a ringcarbon atom:

wherein R^(B2), R^(B3) and R^(B3SN) and the jagged line are as definedabove.

Preferably R^(B2) is selected from the group consisting of methyl,ethyl, n-propyl, trifluoromethyl and difluoroethyl. More preferablyR^(B2) is selected from the group consisting of methyl, ethyl, anddifluoroethyl.

Preferably R^(B3) and/or R^(B3SN) are each independently selected fromchloro, fluoro, bromo, methyl, ethyl, difluoromethyl, trifluoromethylC₁-C₃haloalkoxy, C₁-C₃alkoxy, or C₁-C₃alkyl. The skilled man willappreciate that where Q¹ is trisubstituted, R^(B3) and R^(B3SN) may bethe same or different.

In a third set of embodiments Q¹ is a di-substituted pyrazole ringsystem, and R^(B2) and R^(B3) together with the atoms to which they arejoined and Q¹ form an eight or nine-membered fused hetero-bicyclic ringsystem. In such embodiments R^(B2) is C₁-C₃ alkyl and R^(B3) is selectedfrom C₁-C₃alkyl, C₁-C₃fluoroalkyl, and C₁-C₃haloalkoxy. Examples of suchfused ring systems are shown below as groups Q¹-F1 to Q¹-F12respectively:

Particularly preferred compounds of formula (II) for use as component Bin compositions of the invention are shown below in Table 1. The skilledman will appreciate that Table 1 specifies stereochemistry for compoundsof formula (II). Whilst these are the most preferred stereoisomers forcompounds of formula (II), racemic mixtures of stereoisomers are alsoherbicidal and as such may equally be employed as component B inmixtures of the invention.

TABLE 1 Compounds of formula (II) for use in compositions describedherein. Compound No. Name Structure 2.1 (3S,4R)-N-(2,3-difluorophenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.2  (3S,4R)-N-(2-fluorophenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.3  (3S,4R)-N-(2,4-difluorophenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.4  (3S,4R)-N-[3-fluoro-2- (trifluoromethoxy)phenyl]-1-methyl-4-[1-methyl-5- (trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide

2.5  (3S,4R)-N-[3-fluoro-2- (trifluoromethyl)phenyl]-1-methyl-4-[1-methyl-5- (trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide

2.6  (3S,4R)-N-(3-fluoro-2-methoxy- phenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.7  (3S,4R)-1-methyl-4-[1-methyl-5- (trifluoromethyl)pyrazol-3-yl]-2-oxo-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide

2.8  (3S,4R)-N-(2,6-difluoro-3-pyridyl)- 1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.9  (3S,4R)-N-(6-fluoro-2-pyridyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.10 (3S,4R)-N-[2-(difluoromethoxy)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol- 3-yl]-2-oxo-pyrrolidine-3-carboxamide

2.11 (3S,4R)-N-(2-ethylphenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.12 (3S,4R)-N-[2-(1,1-difluoroethyl)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol- 3-yl]-2-oxo-pyrrolidine-3-carboxamide

2.13 (3S,4R)-N-(2-chloro-3-thienyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.14 (3S,4R)-N-(2-fluoro-3-thienyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.15 (3S,4S)-N-(2,3-difluorophenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-4-yl]-2- oxo-pyrrolidine-3-carboxamide

2.16 (3S,4S)-N-(2-fluorophenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-4-yl]-2- oxo-pyrrolidine-3-carboxamide

2.17 (3S,4S)-N-(2,4-difluorophenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-4-yl]-2- oxo-pyrrolidine-3-carboxamide

2.18 (3S,4S)-N-[3-fluoro-2- (trifluoromethyl)phenyl]-1-methyl-4-[1-methyl-5- (trifluoromethyl)pyrazol-4-yl]-2-oxo-pyrrolidine-3-carboxamide

2.19 (3S,4S)-N-[3-fluoro-2- (trifluoromethyl)phenyl]-1-methyl-4-[1-methyl-5- (trifluoromethyl)pyrazol-4-yl]-2-oxo-pyrrolidine-3-carboxamide

2.20 (3S,4S)-N-(3-fluoro-2-methoxy- phenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-4-yl]-2- oxo-pyrrolidine-3-carboxamide

2.21 (3S,4S)-1-methyl-4-[1-methyl-5- (trifluoromethyl)pyrazol-4-yl]-2-oxo-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide

2.22 (3S,4S)-N-(2,6-difluoro-3-pyridyl)- 1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-4-yl]-2- oxo-pyrrolidine-3-carboxamide

2.23 (3S,4S)-N-[2-(1,1-difluoroethyl)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol- 4-yl]-2-oxo-pyrrolidine-3-carboxamide

2.24 (3S,4S)-N-[2-(difluoromethoxy)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol- 4-yl]-2-oxo-pyrrolidine-3-carboxamide

2.25 (3S,4S)-N-[2-(difluoromethoxy)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol- 4-yl]-2-oxo-pyrrolidine-3-carboxamide

2.26 (3S,4S)-N-(2-ethylphenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-4-yl]-2- oxo-pyrrolidine-3-carboxamide

2.27 (3S,4R)-N-(2-chloro-3-thienyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.28 (3S,4S)-N-(2-fluoro-3-thienyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-4-yl]-2- oxo-pyrrolidine-3-carboxamide

2.29 (3S,4R)-N-(2,3-difluorophenyl)-1- methyl-4-[2-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.30 (3S)-N-(2-fluorophenyl)-1-methyl- 4-[2-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.31 (3S,4R)-N-(2,4-difluorophenyl)-1- methyl-4-[2-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.32 (3S,4R)-N-[3-fluoro-2- (trifluoromethoxy)phenyl]-1-methyl-4-[2-methyl-5- (trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide

2.33 (3S,4R)-N-[3-fluoro-2- (trifluoromethyl)phenyl]-1-methyl-4-[2-methyl-5- (trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide

2.34 (3S,4R)-N-(3-fluoro-2-methoxy- phenyl)-1-methyl-4-[2-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2- oxo-pyrrolidine-3-carboxamide

2.35 (3S,4R)-1-methyl-4-[2-methyl-5- (trifluoromethyl)pyrazol-3-yl]-2-oxo-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide

2.36 (3S,4R)-N-(2,6-difluoro-3-pyridyl)- 1-methyl-4-[1-methyl-3-(trifluoromethyl)-3H-pyrazol-5-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.37 (3S,4R)-N-(6-fluoro-2-pyridyl)-1- methyl-4-[1-methyl-3-(trifluoromethyl)-3H-pyrazol-5-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.38 (3S,4R)-N-[2-(difluoromethoxy)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-3-(trifluoromethyl)-3H- pyrazol-5-yl]-2-oxo-pyrrolidine-3-carboxamide

2.39 (3S,4R)-N-(2-ethylphenyl)-1- methyl-4-[1-methyl-3-(trifluoromethyl)-3H-pyrazol-5-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.40 (3S,4R)-N-[2-(1,1-difluoroethyl)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-3-(trifluoromethyl)-3H- pyrazol-5-yl]-2-oxo-pyrrolidine-3-carboxamide

2.41 (3S,4R)-N-(2-chloro-3-thienyl)-1- methyl-4-[1-methyl-3-(trifluoromethyl)-3H-pyrazol-5-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.42 (3S,4R)-N-(2-fluoro-3-thienyl)-1- methyl-4-[1-methyl-3-(trifluoromethyl)-3H-pyrazol-5-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.43 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(2,3-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.44 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(2-fluorophenyl)-1-methyl-2-oxo-pyrrolidine-3- carboxamide

2.45 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(2,4-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.46 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-[3-fluoro-2-(trifluoromethoxy)phenyl]-1- methyl-2-oxo-pyrrolidine-3- carboxamide

2.47 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-[3-fluoro-2-(trifluoromethyl)phenyl]-1-methyl- 2-oxo-pyrrolidine-3-carboxamide

2.48 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(3-fluoro-2-methoxy-phenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.49 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-1-methyl-2-oxo-N-(2,3,4-trifluorophenyl)pyrrolidine- 3-carboxamide

2.50 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(2,6-difluoro-3-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.51 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(6-fluoro-2-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.52 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-[2-(difluoromethoxy)-3-fluoro- phenyl]-1-methyl-2-oxo-pyrrolidine-3-carboxamide

2.53 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(2-ethylphenyl)-1-methyl-2-oxo-pyrrolidine-3- carboxamide

2.54 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-[2-(1,1-difluoroethyl)-3-fluoro-phenyl]-1- methyl-2-oxo-pyrrolidine-3-carboxamide

2.55 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(2-chloro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.56 (3S,4R)-4-(5-chloro-1-methyl- pyrazol-3-yl)-N-(2-fluoro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.57 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(2,3-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.58 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(2-fluorophenyl)-1-methyl-2-oxo-pyrrolidine-3- carboxamide

2.59 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(2,4-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.60 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-[3-fluoro-2-(trifluoromethoxy)phenyl]-1- methyl-2-oxo-pyrrolidine-3- carboxamide

2.61 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-[3-fluoro-2-(trifluoromethyl)phenyl]-1-methyl- 2-oxo-pyrrolidine-3-carboxamide

2.62 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(3-fluoro-2-methoxy-phenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.63 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-1-methyl-2-oxo-N-(2,3,4-trifluorophenyl)pyrrolidine- 3-carboxamide

2.64 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-(2,6-difluoro-3-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.65 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(6-fluoro-2-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.66 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-[2-(difluoromethoxy)-3-fluoro- phenyl]-1-methyl-2-oxo-pyrrolidine-3-carboxamide

2.67 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(2-ethylphenyl)-1-methyl-2-oxo-pyrrolidine-3- carboxamide

2.68 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-[2-(1,1-difluoroethyl)-3-fluoro-phenyl]-1- methyl-2-oxo-pyrrolidine-3-carboxamide

2.69 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(2-chloro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.70 (3S,4S)-4-(5-chloro-1-methyl- pyrazol-4-yl)-N-(2-fluoro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.71 (3S,4R)-4-(5-chloro-2-methyl- pyrazol-3-yl)-N-(2,3-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.72 (3S)-4-(5-chloro-2-methyl-pyrazol-3-yl)-N-(2-fluorophenyl)-1-methyl- 2-oxo-pyrrolidine-3-carboxamide

2.73 (3S,4R)-4-(5-chloro-2-methyl- pyrazol-3-yl)-N-(2,4-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.74 (3S,4R)-4-(5-chloro-2-methyl- pyrazol-3-yl)-N-[3-fluoro-2-(trifluoromethoxy)phenyl]-1- methyl-2-oxo-pyrrolidine-3- carboxamide

2.75 (3S,4R)-4-(5-chloro-2-methyl- pyrazol-3-yl)-N-[3-fluoro-2-(trifluoromethyl)phenyl]-1-methyl- 2-oxo-pyrrolidine-3-carboxamide

2.76 (3S,4R)-4-(5-chloro-2-methyl- pyrazol-3-yl)-N-(3-fluoro-2-methoxy-phenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.77 (3S,4R)-1-methyl-4-[2-methyl-5- (trifluoromethyl)pyrazol-3-yl]-2-oxo-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide

2.78 (3S,4R)-N-(2,6-difluoro-3-pyridyl)-1-methyl-4-[1-methyl-3-(chorol)- 3H-pyrazol-5-yl]-2-oxo-pyrrolidine-3-carboxamide

2.79 (3S,4R)-N-(6-fluoro-2-pyridyl)-1- methyl-4-[1-methyl-3-(chloro)-3H-pyrazol-5-yl]-2-oxo-pyrrolidine-3- carboxamide

2.80 (3S,4R)-N-[2-(difluoromethoxy)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-3-(chloro)-3H-pyrazol-5-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.81 (3S,4R)-N-(2-ethylphenyl)-1- methyl-4-[1-methyl-3-(chloro)-3H-pyrazol-5-yl]-2-oxo-pyrrolidine-3- carboxamide

2.82 (3S,4R)-N-[2-(1,1-difluoroethyl)-3- fluoro-phenyl]-1-methyl-4-[1-methyl-3-(chloro)-3H-pyrazol-5-yl]- 2-oxo-pyrrolidine-3-carboxamide

2.83 (3S,4R)-N-(2-chloro-3-thienyl)-1- methyl-4-[1-methyl-3-(chloro)-3H-pyrazol-5-yl]-2-oxo-pyrrolidine-3- carboxamide

2.84 (3S,4R)-N-(2-fluoro-3-thienyl)-1- methyl-4-[1-methyl-3-(chloro)-3H-pyrazol-5-yl]-2-oxo-pyrrolidine-3- carboxamide

2.85 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(2,3-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.86 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(2-fluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.87 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(2,4-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.88 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-[3-fluoro-2-(trifluoromethoxy)phenyl]-1- methyl-2-oxo-pyrrolidine-3- carboxamide

2.89 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-[3-fluoro-2-(trifluoromethyl)phenyl]-1-methyl- 2-oxo-pyrrolidine-3-carboxamide

2.90 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(3-fluoro-2-methoxy-phenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.91 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-1-methyl-2-oxo-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide

2.92 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(2,6-difluoro-3-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.93 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(6-fluoro-2-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.94 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-[2-(difluoromethoxy)-3-fluoro- phenyl]-1-methyl-2-oxo-pyrrolidine-3-carboxamide

2.95 ((3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(2-ethylphenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.96 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-[2-(1,1-difluoroethyl)-3-fluoro-phenyl]-1- methyl-2-oxo-pyrrolidine-3-carboxamide

2.97 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(2-chloro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.98 (3S,4R)-4-(4-bromo-5-chloro-1- methyl-pyrazol-3-yl)-N-(2-fluoro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

2.99 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-(2,3-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.100 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-(2-fluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.101 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-(2,4-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.102 (3S,4S)-4-(3-bromo-5-chloro-1-methyl-pyrazol-4-yl)-N-[3-fluoro-2- (trifluoromethoxy)phenyl]-1-methyl-2-oxo-pyrrolidine-3- carboxamide

 2.103 (3S,4S)-4-(3-bromo-5-chloro-1-methyl-pyrazol-4-yl)-N-[3-fluoro-2- (trifluoromethyl)phenyl]-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.104 (3S,4S)-4-(3-bromo-5-chloro-1-methyl-pyrazol-4-yl)-N-(3-fluoro-2- methoxy-phenyl)-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.105 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-1-methyl-2-oxo-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide

 2.106 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-(2,6-difluoro-3-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.107 (3S,4S)-4-(3-bromo-5-chloro-1-methyl-pyrazol-4-yl)-N-(6-fluoro-2- pyridyl)-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.108 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-[2-(difluoromethoxy)-3-fluoro- phenyl]-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.109 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-(2-ethylphenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.110 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-[2-(1,1-difluoroethyl)-3-fluoro-phenyl]-1- methyl-2-oxo-pyrrolidine-3-carboxamide

 2.111 (3S,4S)-4-(3-bromo-5-chloro-1- methyl-pyrazol-4-yl)-N-(2-chloro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.112 (3S,4S)-4-(3-bromo-5-chloro-1-methyl-pyrazol-4-yl)-N-(2-fluoro-3- thienyl)-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.113 (3S,4R)-4-(4-bromo-5-chloro-2- methyl-pyrazol-3-yl)-N-(2,3-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.114 (3S)-4-(4-bromo-5-chloro-2- methyl-pyrazol-3-yl)-N-(2-fluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.115 (3S,4R)-4-(4-bromo-5-chloro-2- methyl-pyrazol-3-yl)-N-(2,4-difluorophenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.116 (3S,4R)-4-(4-bromo-5-chloro-2-methyl-pyrazol-3-yl)-N-[3-fluoro-2- (trifluoromethoxy)phenyl]-1-methyl-2-oxo-pyrrolidine-3- carboxamide

 2.117 (3S,4R)-4-(4-bromo-5-chloro-2-methyl-pyrazol-3-yl)-N-[3-fluoro-2- (trifluoromethyl)phenyl]-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.118 (3S,4R)-4-(4-bromo-5-chloro-2-methyl-pyrazol-3-yl)-N-(3-fluoro-2- methoxy-phenyl)-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.119 (3S,4R)-4-(4-bromo-5-chloro-2- methyl-pyrazol-3-yl)-1-methyl-2-oxo-N-(2,3,4- trifluorophenyl)pyrrolidine-3- carboxamide

 2.120 (3S,4R)-4-(4-bromo-3-chloro-1- methyl-3H-pyrazol-5-yl)-N-(2,6-difluoro-3-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.121 (3S,4R)-4-(4-bromo-3-chloro-1- methyl-3H-pyrazol-5-yl)-N-(6-fluoro-2-pyridyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.122 (3S,4R)-4-(4-bromo-3-chloro-1- methyl-3H-pyrazol-5-yl)-N-[2-(difluoromethoxy)-3-fluoro- phenyl]-1-methyl-2-oxo-pyrrolidine-3-carboxamide

 2.123 (3S,4R)-4-(4-bromo-3-chloro-1- methyl-3H-pyrazol-5-yl)-N-(2-ethylphenyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

 2.124 (3S,4R)-4-(4-bromo-3-chloro-1- methyl-3H-pyrazol-5-yl)-N-[2-(1,1-difluoroethyl)-3-fluoro-phenyl]-1- methyl-2-oxo-pyrrolidine-3-carboxamide

 2.125 (3S,4R)-4-(4-bromo-3-chloro-1- methyl-3H-pyrazol-5-yl)-N-(2-chloro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

   2.126I (3S,4R)-4-(4-bromo-3-chloro-1- methyl-3H-pyrazol-5-yl)-N-(2-fluoro-3-thienyl)-1-methyl-2-oxo- pyrrolidine-3-carboxamide

In one embodiment B is compound 2.1.

In one embodiment B is compound 2.2.

In one embodiment B is compound 2.3.

In one embodiment B is compound 2.4.

In one embodiment B is compound 2.5.

In one embodiment B is compound 2.6.

In one embodiment B is compound 2.7.

In one embodiment B is compound 2.8.

In one embodiment B is compound 2.9.

In one embodiment B is compound 2.10.

In one embodiment B is compound 2.11.

In one embodiment B is compound 2.12.

In one embodiment B is compound 2.13.

In one embodiment B is compound 2.14.

In one embodiment B is compound 2.15.

In one embodiment B is compound 2.16.

In one embodiment B is compound 2.17.

In one embodiment B is compound 2.18.

In one embodiment B is compound 2.19.

In one embodiment B is compound 2.20.

In one embodiment B is compound 2.21.

In one embodiment B is compound 2.22.

In one embodiment B is compound 2.23.

In one embodiment B is compound 2.24.

In one embodiment B is compound 2.25.

In one embodiment B is compound 2.26.

In one embodiment B is compound 2.27.

In one embodiment B is compound 2.28.

In one embodiment B is compound 2.29.

In one embodiment B is compound 2.30.

In one embodiment B is compound 2.31.

In one embodiment B is compound 2.32.

In one embodiment B is compound 2.33.

In one embodiment B is compound 2.34.

In one embodiment B is compound 2.35.

In one embodiment B is compound 2.36

In one embodiment B is compound 2.37

In one embodiment B is compound 2.38

In one embodiment B is compound 2.39.

In one embodiment B is compound 2.40.

In one embodiment B is compound 2.41.

In one embodiment B is compound 2.42.

In one embodiment B is compound 2.43.

In one embodiment B is compound 2.44

In one embodiment B is compound 2.45.

In one embodiment B is compound 2.46.

In one embodiment B is compound 2.47.

In one embodiment B is compound 2.48.

In one embodiment B is compound 2.49.

In one embodiment B is compound 2.50.

In one embodiment B is compound 2.51.

In one embodiment B is compound 2.52.

In one embodiment B is compound 2.53.

In one embodiment B is compound 2.54.

In one embodiment B is compound 2.55.

In one embodiment B is compound 2.56.

In one embodiment B is compound 2.57.

In one embodiment B is compound 2.58.

In one embodiment B is compound 2.59.

In one embodiment B is compound 2.60.

In one embodiment B is compound 2.61.

In one embodiment B is compound 2.62.

In one embodiment B is compound 2.63.

In one embodiment B is compound 2.64.

In one embodiment B is compound 2.65.

In one embodiment B is compound 2.66.

In one embodiment B is compound 2.67.

In one embodiment B is compound 2.68.

In one embodiment B is compound 2.69.

In one embodiment B is compound 2.70.

In one embodiment B is compound 2.71.

In one embodiment B is compound 2.72.

In one embodiment B is compound 2.73.

In one embodiment B is compound 2.74

In one embodiment B is compound 2.75.

In one embodiment B is compound 2.76.

In one embodiment B is compound 2.77.

In one embodiment B is compound 2.78.

In one embodiment B is compound 2.79.

In one embodiment B is compound 2.80.

In one embodiment B is compound 2.81.

In one embodiment B is compound 2.82.

In one embodiment B is compound 2.83

In one embodiment B is compound 2.84.

In one embodiment B is compound 2.85.

In one embodiment B is compound 2.86.

In one embodiment B is compound 2.87.

In one embodiment B is compound 2.88.

In one embodiment B is compound 2.89.

In one embodiment B is compound 2.90.

In one embodiment B is compound 2.91

In one embodiment B is compound 2.92.

In one embodiment B is compound 2.93

In one embodiment B is compound 2.94

In one embodiment B is compound 2.95.

In one embodiment B is compound 2.96.

In one embodiment B is compound 2.97.

In one embodiment B is compound 2.98.

In one embodiment B is compound 2.99

In one embodiment B is compound 2.100.

In one embodiment B is compound 2.101.

In one embodiment B is compound 2.102.

In one embodiment B is compound 2.103.

In one embodiment B is compound 2.104.

In one embodiment B is compound 2.105.

In one embodiment B is compound 2.106.

In one embodiment B is compound 2.107.

In one embodiment B is compound 2.108.

In one embodiment B is compound 2.109.

In one embodiment B is compound 2.110.

In one embodiment B is compound 2.111.

In one embodiment B is compound 2.112.

In one embodiment B is compound 2.113.

In one embodiment B is compound 2.114.

In one embodiment B is compound 2.115.

In one embodiment B is compound 2.116.

In one embodiment B is compound 2.117.

In one embodiment B is compound 2.118.

In one embodiment B is compound 2.119.

In one embodiment B is compound 2.120.

In one embodiment B is compound 2.121.

In one embodiment B is compound 2.122.

In one embodiment B is compound 2.123.

In one embodiment B is compound 2.124.

In one embodiment B is compound 2.125.

In one embodiment B is compound 2.126.

Compounds of formula (II) as described herein may be made as describedin WO2015/084796 as well as by the racemic synthesis route andasymmetric synthesis route as described herein in the PreparationExamples.

The starting materials used for the preparation of the compoundsemployed in the invention may be purchased from usual commercialsuppliers or may be prepared by known methods. The starting materials aswell as the intermediates may be purified before use in the next WO2015/193202 step by state of the art methodologies such aschromatography, crystallization, distillation and filtration.

Crops of useful plants in which the composition according to theinvention can be used include perennial and annual crops, such as berryplants for example blackberries, blueberries, cranberries, raspberriesand strawberries; cereals for example barley, maize (corn), millet,oats, rice, rye, sorghum triticale and wheat; fibre plants for examplecotton, flax, hemp, jute and sisal; field crops for example sugar andfodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees for example apple,apricot, avocado, banana, cherry, citrus, nectarine, peach, pear andplum; grasses for example Bermuda grass, bluegrass, bentgrass, centipedegrass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbssuch as basil, borage, chives, coriander, lavender, lovage, mint,oregano, parsley, rosemary, sage and thyme; legumes for example beans,lentils, peas and soya beans; nuts for example almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palms for exampleoil palm; ornamentals for example flowers, shrubs and trees; othertrees, for example cacao, coconut, olive and rubber; vegetables forexample asparagus, aubergine, broccoli, cabbage, carrot, cucumber,garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin,rhubarb, spinach and tomato; and vines for example grapes.

Crops are to be understood as being those which are naturally occurring,obtained by conventional methods of breeding, or obtained by geneticengineering. They include crops which contain so-called output traits(e.g. improved storage stability, higher nutritional value and improvedflavour).

Crops are to be understood as also including those crops which have beenrendered tolerant to herbicides like bromoxynil or classes of herbicidessuch as ALS-, EPSPS-, GS-, HPPD- and PPO-inhibitors. An example of acrop that has been rendered tolerant to imidazolinones, e.g. imazamox,by conventional methods of breeding is Clearfield® summer canola.Examples of crops that have been rendered tolerant to herbicides bygenetic engineering methods include e.g. glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

Crops are also to be understood as being those which naturally are orhave been rendered resistant to harmful insects. This includes plantstransformed by the use of recombinant DNA techniques, for example, to becapable of synthesising one or more selectively acting toxins, such asare known, for example, from toxin-producing bacteria. Examples oftoxins which can be expressed include 6-endotoxins, vegetativeinsecticidal proteins (Vip), insecticidal proteins of bacteriacolonising nematodes, and toxins produced by scorpions, arachnids, waspsand fungi.

An example of a crop that has been modified to express the Bacillusthuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). Anexample of a crop comprising more than one gene that codes forinsecticidal resistance and thus expresses more than one toxin isVipCot® (Syngenta Seeds). Crops or seed material thereof can also beresistant to multiple types of pests (so-called stacked transgenicevents when created by genetic modification). For example, a plant canhave the ability to express an insecticidal protein while at the sametime being herbicide tolerant, for example Herculex I® (DowAgroSciences, Pioneer Hi-Bred International).

Compositions of the invention can typically be used to control a widevariety of monocotyledonous and dicotyledonous weed species. Examples ofmonocotyledonous species that can typically be controlled includeAlopecurus myosuroides, Avena fatua, Brachiaria plantaginea, Bromustectorum, Cyperus esculentus, Digitaria sanguinalis, Echinochloacrus-galli, Lolium perenne, Lolium multiflorum, Panicum miliaceum, Poaannua, Setaria viridis, Setaria faberi and Sorghum bicolor. Examples ofdicotyledonous species that can be controlled include Abutilontheophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album,Euphorbia heterophylla, Galium aparine, Ipomoea hederacea, Kochiascoparia, Polygonum convolvulus, Sida spinosa, Sinapis arvensis, Solanumnigrum, Stellaria media, Veronica persica and Xanthium strumarium.

In all aspects of the invention, in any particular embodiment, theweeds, e.g. to be controlled and/or growth-inhibited, may bemonocotyledonous or dicotyledonous weeds, which are tolerant orresistant to one or more other herbicides for example, HPPD inhibitorherbicides such as mesotrione, PSII inhibitor herbicides such asatrazine or EPSPS inhibitors such as glyphosate. Such weeds include, butare not limited to resistant Amaranthus biotypes.

Compositions of this invention can also be mixed with one or morefurther pesticides including herbicides [typically different to theherbicides of formula (l) and formula (II)], fungicides, insecticides,nematocides, bactericides, acaricides, growth regulators,chemosterilants, semiochemicals, repellents, attractants, pheromones,feeding stimulants or other biologically active compounds to form amulti-component pesticide giving an even broader spectrum ofagricultural protection.

Similarly compositions of the invention (which includes those comprisingone or more additional pesticide as described in the precedingparagraph) can further include one or more safeners. In particular, thefollowing safeners are especially preferred: AD 67 (MON 4660),benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfamide, dichlormid,dicyclonon, dietholate, fenchlorazole-ethyl, fenclorim, flurazole,fluxofenim, furilazole, furilazome, isoxadifen-ethyl, mefenpyr-diethyl,mephenate, oxabetrinil, naphthalic anhydride (CAS RN 81-84-5), TI-35,N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN221668-34-4) andN-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.Such safeners may also be used in the form of esters or salts, asmentioned e.g. in The Pesticide Manual, 15th Ed. (BCPC), 2009. Thus, thereference to cloquintocet-mexyl also applies to cloquintocet and to alithium, sodium, potassium, calcium, magnesium, aluminium, iron,ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof asdisclosed in WO02/34048 and the reference to fenchlorazole-ethyl alsoapplies to fenchlorazole, etc.

In general, the mixing ratio (by weight) of the compound of formula (I)to the compound of formula (II) is from 0.01:1 to 100:1, more preferablyfrom 0.05:1 to 20:1, even more preferably from 0.1:1 to 20:1 and mostpreferably from 0.2:1 to 20:1, for example, 0.3125:1, 0.625:1, 1:1,1.25:1, 2.5:1, 5:1, 10:1 and 20:1.

The amount of a composition according to the invention to be applied,will depend on various factors, such as the compounds employed; thesubject of the treatment, such as, for example the plants (crops and/orweeds), soil or seeds; the part of the plant to which the treatment isapplied (e.g. foliar application, drench, in-furrow application) thetype of treatment, such as, for example spraying, dusting or seeddressing; the application timing (pre- or post-emergence).

When applied per se to the useful plants, or the locus thereof,component (A) may be applied at a rate of 50 to 2000 g a. i./ha,particularly 100 to 1000 g a. i./ha and more particularly 300 to 500 ga. i./ha e.g. 300, 350, 400, 450 or 500 g a. i./ha. However, in certainembodiments, component (A) is preferably applied lower rates of 5 to 25g a. i./ha, in particular at 5, 10, 15, 20 or 25 g a. i./ha.

Component (B), i.e. a compound of formula (II), when used per se, istypically applied at a rate of from 5 to 2000 g a. i./ha. In particular,it may be applied at a rate of 10, 25, 30, 60, 75, 100, 125, 200, 250,300, 350, 400, 450, 500 or 1000 g a. i./ha.

In agricultural practice the application rates of the compositionaccording to the invention depend on the type of effect desired, andtypically range from 10 to 4000 g of total composition per hectare. Thusin particular compositions of the invention component (A) may be appliedat a rate of 5, 10, 15, 20, 25, 50, 300, 350, 400, 450 or 500 g a.i./ha, typically in association with component B at a rate of 10, 25,30, 60, 75, 100, 125, 200, 250, 300, 350, 400, 450, 500 or 1000 g a.i./ha.

The compounds of the invention can be applied before or after plantingof the crops, before weeds emerge (pre-emergence application) or afterweeds emerge (post-emergence application) and are particularly effectivewhen applied pre-emergence to the weeds.

Where a safener is combined with mixtures of the invention, it ispreferred that the mixing ratio of compound of formula (I) to safener isfrom 100:1 to 1:10, especially from 20:1 to 1:1.

It is possible that the safener and the compositions of the inventionare applied simultaneously. For example, the safener and the compositionof the invention might be applied to the locus pre-emergence or might beapplied to the crop post-emergence. It is also possible that the safenerand the composition of the invention are applied sequentially. Forexample, the safener might be applied before sowing the seeds as a seedtreatment and the composition of the invention might be applied to thelocus pre-emergence or might be applied to the crop post-emergence.

The compositions of the invention can advantageously be used in thebelow-mentioned formulations (in which case “active ingredient” relatesto the respective mixture of compound of formula (I) with a compound offormula (II) or, when a safener is also used, the respective mixture ofthe compound of formula (I) with the compound of formula (II) and thesafener).

The individual components of the composition of the invention may beutilised as the technical active ingredient as produced. More typicallyhowever, the compositions according to the invention may be formulatedin various ways using formulation adjuvants, such as carriers, solventsand surface-active substances. The formulations can be in variousphysical forms, e.g. in the form of dusting powders, gels, wettablepowders, water-dispersible granules, water-dispersible tablets,effervescent pellets, emulsifiable concentrates, microemulsifiableconcentrates, oil-in-water emulsions, oil-flowables, aqueousdispersions, oily dispersions, suspo-emulsions, capsule suspensions,emulsifiable granules, soluble liquids, water-soluble concentrates (withwater or a water-miscible organic solvent as carrier), impregnatedpolymer films or in other forms known e.g. from the Manual onDevelopment and Use of FAO and WHO Specifications for Pesticides, UnitedNations, First Edition, Second Revision (2010). Such formulations caneither be used directly or diluted prior to use. The dilutions can bemade, for example, with water, liquid fertilisers, micronutrients,biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredientwith the formulation adjuvants in order to obtain compositions in theform of finely divided solids, granules, solutions, dispersions oremulsions. The active ingredients can also be formulated with otheradjuvants, such as finely divided solids, mineral oils, oils ofvegetable or animal origin, modified oils of vegetable or animal origin,organic solvents, water, surface-active substances or combinationsthereof.

The active ingredients can also be contained in very fine microcapsules.Microcapsules contain the active ingredients in a porous carrier. Thisenables the active ingredients to be released into the environment incontrolled amounts (e.g. slow-release). Microcapsules usually have adiameter of from 0.1 to 500 microns. They contain active ingredients inan amount of about from 25 to 95% by weight of the capsule weight. Theactive ingredients can be in the form of a monolithic solid, in the formof fine particles in solid or liquid dispersion or in the form of asuitable solution. The encapsulating membranes can comprise, forexample, natural or synthetic rubbers, cellulose, styrene/butadienecopolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides,polyureas, polyurethane or chemically modified polymers and starchxanthates or other polymers that are known to the person skilled in theart. Alternatively, very fine microcapsules can be formed in which theactive ingredient is contained in the form of finely divided particlesin a solid matrix of base substance, but the microcapsules are notthemselves encapsulated.

The formulation adjuvants that are suitable for the preparation of thecompositions according to the invention are known per se. As liquidcarriers there may be used: water, toluene, xylene, petroleum ether,vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acidanhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone,butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkylesters of acetic acid, diacetone alcohol, 1,2-dichloropropane,diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycolabietate, diethylene glycol butyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, N,N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methylether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone,ethyl acetate, 2-ethylhexanol, ethylene carbonate,1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyllactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycolmethyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glyceroldiacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamylacetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene,isopropyl myristate, lactic acid, laurylamine, mesityl oxide,methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyllaurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene,n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleicacid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid,propyl lactate, propylene carbonate, propylene glycol, propylene glycolmethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol,xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propyleneglycol methyl ether, diethylene glycol methyl ether, methanol, ethanol,isopropanol, and alcohols of higher molecular weight, such as amylalcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol,propylene glycol, glycerol, N-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone,calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks,wheat flour, soybean flour, pumice, wood flour, ground walnut shells,lignin and similar substances.

A large number of surface-active substances can advantageously be usedin both solid and liquid formulations, especially in those formulationswhich can be diluted with a carrier prior to use. Surface-activesubstances may be anionic, cationic, non-ionic or polymeric and they canbe used as emulsifiers, wetting agents or suspending agents or for otherpurposes. Typical surface-active substances include, for example, saltsof alkyl sulfates, such as diethanolammonium lauryl sulfate; salts ofalkylarylsulfonates, such as calcium dodecylbenzenesulfonate;alkylphenol/alkylene oxide addition products, such as nonylphenolethoxylate; alcohol/alkylene oxide addition products, such astridecylalcohol ethoxylate; soaps, such as sodium stearate; salts ofalkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate;dialkyl esters of sulfosuccinate salts, such as sodiumdi(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitololeate; quaternary amines, such as lauryltrimethylammonium chloride,polyethylene glycol esters of fatty acids, such as polyethylene glycolstearate; block copolymers of ethylene oxide and propylene oxide; andsalts of mono and di-alkylphosphate esters; and also further substancesdescribed e.g. in McCutcheon's Detergents and Emulsifiers Annual, MCPublishing Corp., Ridgewood N.J. (1981).

Further adjuvants that can be used in pesticidal formulations includecrystallisation inhibitors, viscosity modifiers, suspending agents,dyes, anti-oxidants, foaming agents, light absorbers, mixingauxiliaries, antifoams, complexing agents, neutralising or pH-modifyingsubstances and buffers, corrosion inhibitors, fragrances, wettingagents, take-up enhancers, micronutrients, plasticisers, glidants,lubricants, dispersants, thickeners, antifreezes, microbicides, andliquid and solid fertilisers.

The formulations according to the invention can include an additivecomprising an oil of vegetable or animal origin, a mineral oil, alkylesters of such oils or mixtures of such oils and oil derivatives. Theamount of oil additive in the composition according to the invention isgenerally from 0.01 to 10%, based on the mixture to be applied. Forexample, the oil additive can be added to a spray tank in the desiredconcentration after a spray mixture has been prepared. Preferred oiladditives comprise mineral oils or an oil of vegetable origin, forexample rapeseed oil, olive oil or sunflower oil, emulsified vegetableoil, alkyl esters of oils of vegetable origin, for example the methylderivatives, or an oil of animal origin, such as fish oil or beeftallow. Preferred oil additives comprise alkyl esters of C₈C₂₂ fattyacids, especially the methyl derivatives of C₁₂-C₁₈ fatty acids, forexample the methyl esters of lauric acid, palmitic acid and oleic acid(methyl laurate, methyl palmitate and methyl oleate, respectively). Manyoil derivatives are known from the Compendium of Herbicide Adjuvants,10^(th) Edition, Southern Illinois University, 2010.

The formulations generally comprise from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of compounds (A) and (B) and from1 to 99.9% by weight of a formulation adjuvant which preferably includesfrom 0 to 25% by weight of a surface-active substance. Whereascommercial products may preferably be formulated as concentrates, theend user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on thenature of the soil, the method of application, the crop plant, the pestto be controlled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. As a general guideline compounds may be applied at a rateof from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %),wherein the term “active ingredient” refers to the total weight % of thecombination of all active ingredients in the composition:

Emulsifiable Concentrates:

active ingredient: 1 to 95%, preferably 60 to 90%

surface-active agent: 1 to 30%, preferably 5 to 20%

liquid carrier: 1 to 80%, preferably 1 to 35%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 5%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surface-active agent: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surface-active agent: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 95%, preferably 15 to 90%

Granules:

active ingredient: 0.1 to 30%, preferably 0.1 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

The following Examples further illustrate, but do not limit, theinvention.

Wettable powders a) b) c) active ingredients 25% 50% 75% sodiumlignosulfonate  5%  5% — sodium lauryl sulphate  3% —  5% sodiumdiisobutylnaphthalenesulfonate —  6% 10% phenol polyethylene glycolether —  2% — (7-8 mol of ethylene oxide) highly dispersed silicic acid 5% 10% 10% Kaolin 62% 27% —The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording wettable powders thatcan be diluted with water to give suspensions of the desiredconcentration.

Powders for dry seed treatment a) b) c) active ingredients 25% 50% 75 %light mineral oil  5%  5%  5% highly dispersed silicic acid  5%  5% —Kaolin 65% 40% — Talcum — 20The combination is thoroughly mixed with the adjuvants and the mixtureis thoroughly ground in a suitable mill, affording powders that can beused directly for seed treatment.

Emulsifiable concentrate active ingredients 10% octylphenol polyethyleneglycol ether  3% (4-5 mol of ethylene oxide)   calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether (35 mol ofethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredients  5%  6%  4% Talcum 95% — — Kaolin —94% — mineral filler — — 96%Ready-for-use dusts are obtained by mixing the combination with thecarrier and grinding the mixture in a suitable mill. Such powders canalso be used for dry dressings for seed.

Extruded granules Active ingredients 15% sodium lignosulfonate  2%Carboxymethylcellulose  1% Kaolin 82%The combination is mixed and ground with the adjuvants, and the mixtureis moistened with water. The mixture is extruded and then dried in astream of air.

Coated granules Active ingredients  8% polyethylene glycol (mol. wt.200)  3% Kaolin 89%The finely ground combination is uniformly applied, in a mixer, to thekaolin moistened with polyethylene glycol. Non-dusty coated granules areobtained in this manner.

Suspension concentrate active ingredients 40% propylene glycol 10%nonylphenol polyethylene glycol ether  6% (15 mol of ethylene oxide)Sodium lignosulfonate 10% Carboxymethylcellulose  1% silicone oil (inthe form of a 75% emulsion in water)  1% Water 32%The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.

Flowable concentrate for seed treatment active ingredients   40%propylene glycol    5% copolymer butanol PO/EO    2% Tristyrenephenolewith 10-20 moles EO    2% 1,2-benzisothiazolin-3-one (in the form  0.5%of a 20% solution in water) monoazo-pigment calcium salt   5% Siliconeoil (in the form of a 75% emulsion in water)  0.2% Water 45.3%The finely ground combination is intimately mixed with the adjuvants,giving a suspension concentrate from which suspensions of any desireddilution can be obtained by dilution with water. Using such dilutions,living plants as well as plant propagation material can be treated andprotected against infestation by microorganisms, by spraying, pouring orimmersion.Slow Release Capsule Suspension

28 Parts of the combination are mixed with 2 parts of an aromaticsolvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed. The obtainedcapsule suspension is stabilized by adding 0.25 parts of a thickener and3 parts of a dispersing agent. The capsule suspension formulationcontains 28% of the active ingredients. The medium capsule diameter is8-15 microns. The resulting formulation is applied to seeds as anaqueous suspension in an apparatus suitable for that purpose.

In one set of embodiments, the composition of the invention willcomprise A and B as described in Table 2 below. Particularly preferredcompositions of the invention are those from Table 2, comprising acompound of formula (II) as described herein in the Examples.

TABLE 2 Compositions of the Invention A B Com- Cmpd Cmpd posi- of ofMore tion for- for- Typical Preferred Preferred Num- mula mula WeightWeight Weight ber (I) (II) Ratio Ratio Ratio 1 1.1 2.1 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 2 1.1 2.2 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 3 1.1 2.3 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 41.1 2.4 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 5 1.1 2.5 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 6 1.1 2.6 0.01:1 to 100:1 0.05:1 to20:1 0.1:1 to 20:1 7 1.1 2.7 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to20:1 8 1.1 2.8 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 9 1.1 2.90.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 10 1.1 2.10 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 11 1.1 2.11 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 12 1.1 2.12 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:113 1.1 2.13 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 14 1.1 2.140.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 15 1.1 2.15 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 16 1.1 2.16 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 17 1.1 2.17 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:118 1.1 2.18 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 19 1.1 2.190.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 20 1.1 2.20 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 21 1.1 2.21 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 22 1.1 2.22 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:123 1.1 2.23 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 24 1.1 2.240.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 25 1.1 2.25 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 26 1.1 2.26 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 27 1.1 2.27 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:128 1.1 2.28 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 29 1.1 2.290.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 30 1.1 2.30 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 31 1.1 2.31 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 32 1.1 2.32 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:133 1.1 2.33 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 34 1.1 2.340.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 35 1.1 2.35 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 36 1.1 2.36 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 37 1.1 2.37 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:138 1.1 2.38 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 39 1.1 2.390.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 40 1.1 2.40 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 41 1.1 2.41 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 42 1.1 2.42 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:143 1.1 2.43 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 44 1.1 2.440.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 45 1.1 2.45 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 46 1.1 2.46 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 47 1.1 2.47 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:148 1.1 2.48 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 49 1.1 2.490.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 50 1.1 2.50 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 51 1.1 2.51 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 52 1.1 2.52 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:153 1.1 2.53 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 54 1.1 2.540.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 55 1.1 2.55 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 56 1.1 2.56 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 57 1.1 2.57 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:158 1.1 2.58 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 59 1.1 2.590.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 60 1.1 2.60 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 61 1.1 2.61 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 62 1.1 2.62 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:163 1.1 2.63 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 64 1.1 2.640.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 65 1.1 2.65 0.01:1 to 100:10.05:1 to 20:1 0.1:1 to 20:1 66 1.1 2.66 0.01:1 to 100:1 0.05:1 to 20:10.1:1 to 20:1 67 1.1 2.67 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:168 1.1 2.68 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 69 1.1 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0.05:1to 20:1 0.1:1 to 20:1 349 1.3 2.97 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 350 1.3 2.98 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 3511.3 2.99 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 352 1.3 2.1000.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 353 1.3 2.101 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 354 1.3 2.102 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 355 1.3 2.103 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 356 1.3 2.104 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 3571.3 2.105 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 358 1.3 2.1060.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 359 1.3 2.107 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 360 1.3 2.108 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 361 1.3 2.109 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 362 1.3 2.110 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 3631.3 2.111 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 364 1.3 2.1120.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 365 1.3 2.113 0.01:1 to100:1 0.05:1 to 20:1 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1.4 2.5 0.01:1 to 100:1 0.05:1 to20:1 0.1:1 to 20:1 384 1.4 2.6 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to20:1 385 1.4 2.7 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 386 1.42.8 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 387 1.4 2.9 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 388 1.4 2.10 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 389 1.4 2.11 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 390 1.4 2.12 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 3911.4 2.13 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 392 1.4 2.140.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 393 1.4 2.15 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 394 1.4 2.16 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 395 1.4 2.17 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 396 1.4 2.18 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 3971.4 2.19 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 398 1.4 2.200.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 399 1.4 2.21 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 400 1.4 2.22 0.01:1 to 100:1 0.05:1to 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to 20:1 6101.5 2.106 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 611 1.5 2.1070.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 612 1.5 2.108 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 613 1.5 2.109 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 614 1.5 2.110 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 615 1.5 2.111 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6161.5 2.112 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 617 1.5 2.1130.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 618 1.5 2.114 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 619 1.5 2.115 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 620 1.5 2.116 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 621 1.5 2.117 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6221.5 2.118 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 623 1.5 2.1190.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 624 1.5 2.120 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 625 1.5 2.121 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 626 1.5 2.122 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 627 1.5 2.123 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6281.5 2.124 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 629 1.5 2.1250.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 630 1.5 2.126 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 631 1.6 2.1 0.01:1 to 100:1 0.05:1 to20:1 0.1:1 to 20:1 632 1.6 2.2 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to20:1 633 1.6 2.3 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 634 1.62.4 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 635 1.6 2.5 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 636 1.6 2.6 0.01:1 to 100:1 0.05:1 to20:1 0.1:1 to 20:1 637 1.6 2.7 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to20:1 638 1.6 2.8 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 639 1.62.9 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 640 1.6 2.10 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 641 1.6 2.11 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 642 1.6 2.12 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 643 1.6 2.13 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6441.6 2.14 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 645 1.6 2.150.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 646 1.6 2.16 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 647 1.6 2.17 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 648 1.6 2.18 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 649 1.6 2.19 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6501.6 2.20 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 651 1.6 2.210.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 652 1.6 2.22 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 653 1.6 2.23 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 654 1.6 2.24 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 655 1.6 2.25 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6561.6 2.26 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 657 1.6 2.270.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 658 1.6 2.28 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 659 1.6 2.29 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 660 1.6 2.30 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 661 1.6 2.31 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6621.6 2.32 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 663 1.6 2.330.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 664 1.6 2.34 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 665 1.6 2.35 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 666 1.6 2.36 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 667 1.6 2.37 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6681.6 2.38 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 669 1.6 2.390.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 670 1.6 2.40 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 671 1.6 2.41 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 672 1.6 2.42 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 673 1.6 2.43 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6741.6 2.44 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 675 1.6 2.450.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 676 1.6 2.46 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 677 1.6 2.47 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 678 1.6 2.48 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 679 1.6 2.49 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6801.6 2.50 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 681 1.6 2.510.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 682 1.6 2.52 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 683 1.6 2.53 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 684 1.6 2.54 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 685 1.6 2.55 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6861.6 2.56 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 687 1.6 2.570.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 688 1.6 2.58 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 689 1.6 2.59 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 690 1.6 2.60 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 691 1.6 2.61 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6921.6 2.62 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 693 1.6 2.630.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 694 1.6 2.64 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 695 1.6 2.65 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 696 1.6 2.66 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 697 1.6 2.67 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 6981.6 2.68 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 699 1.6 2.690.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 700 1.6 2.70 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 701 1.6 2.71 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 702 1.6 2.72 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 703 1.6 2.73 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7041.6 2.74 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 705 1.6 2.750.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 706 1.6 2.76 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 707 1.6 2.77 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 708 1.6 2.78 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 709 1.6 2.79 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7101.6 2.80 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 711 1.6 2.810.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 712 1.6 2.82 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 713 1.6 2.83 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 714 1.6 2.84 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 715 1.6 2.85 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7161.6 2.86 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 717 1.6 2.870.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 718 1.6 2.88 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 719 1.6 2.89 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 720 1.6 2.90 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 721 1.6 2.91 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7221.6 2.92 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 723 1.6 2.930.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 724 1.6 2.94 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 725 1.6 2.95 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 726 1.6 2.96 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 727 1.6 2.97 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7281.6 2.98 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 729 1.6 2.990.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 730 1.6 2.100 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 731 1.6 2.101 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 732 1.6 2.102 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 733 1.6 2.103 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7341.6 2.104 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 735 1.6 2.1050.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 736 1.6 2.106 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 737 1.6 2.107 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 738 1.6 2.108 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 739 1.6 2.109 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7401.6 2.110 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 741 1.6 2.1110.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 742 1.6 2.112 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 743 1.6 2.113 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 744 1.6 2.114 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 745 1.6 2.115 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7461.6 2.116 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 747 1.6 2.1170.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 748 1.6 2.118 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 749 1.6 2.119 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 750 1.6 2.120 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1 751 1.6 2.121 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 7521.6 2.122 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 753 1.6 2.1230.01:1 to 100:1 0.05:1 to 20:1 0.1:1 to 20:1 754 1.6 2.124 0.01:1 to100:1 0.05:1 to 20:1 0.1:1 to 20:1 755 1.6 2.125 0.01:1 to 100:1 0.05:1to 20:1 0.1:1 to 20:1 756 1.6 2.126 0.01:1 to 100:1 0.05:1 to 20:1 0.1:1to 20:1

The skilled man will appreciate that the most preferred ratio range ofA:B for any one of composition numbers 1 to 756 described in Table 2above is from 0.2:1 to 20:1, and that each one of composition numbers 1to 756 described in Table 2 may used at the ratio of A:B of 0.3125:1, orat the ratio of A:B of 0.625:1, or at the ratio of A:B of 1.25:1, or atthe ratio of A:B of 2.5:1, or at the ratio of A:B of 5:1, or at theratio of A:B of 10:1, or at the ratio of A:B of 20:1.

Whilst 756 two-way mixtures of a compound of formula (I) and anotherherbicide are explicitly disclosed above, the skilled man willappreciate that the invention extends to three-way and further multiplecombinations comprising the above two-way mixtures. In particular, thepresent invention provides compositions comprising the three-waymixtures, wherein each of the 2-way mixtures described in Table 2 above,is combined with (a) mesotrione (mixtures 3a1 to 3a756, respectively);(b) bicyclopyrone (mixtures 3b1 to 3b756, respectively); (c) atrazine(mixtures 3c1 to 3c756, respectively); (d) S-metholachlor (mixtures 3d1to 3d756, respectively); (e) terbuthylazine (mixtures 3e1 to 3e756,respectively); (f) dimethaclor (mixtures 3f1 to 3f756, respectively);(g) flufenacet (mixtures 3g1 to 3g756, respectively); (h) glyphosate(mixtures 3h1 to 3h756, respectively); (i)isoxaflutole (mixtures 3i1 to3i756, respectively); (j) nicosulfuron (mixtures 3j1 to 3j756,respectively); (k) ametryn (mixtures 3k1 to 3k756, respectively); (I)hexazinone (mixtures 3l1 to 3l756, respectively); (m) paraquat (mixtures3m1 to 3m756, respectively); (n) diquat (mixtures 3n1 to 3n756,respectively); (o) pyridate (mixtures 3o1 to 3o756, respectively); (p)acetochlor (mixtures 3p1 to 3p756, respectively); (q) dimethenamid-P(mixtures 3q1 to 3q756, respectively); (r) alachlor (mixtures 3r1 to3r756, respectively); (s) pethoxamid (mixtures 3s1 to 3s756,respectively); (t) pyroxosulfone (mixtures 3t1 to 3t756, respectively);(u) trifloxysulfuron sodium (mixtures 3u1 to 3u756, respectively); (v)flazasulfuron (mixtures 3v1 to 3v756, respectively); (w) prosulfocarb(mixtures 3w1 to 3w756, respectively); (x) metolachlor (mixtures 3x1 to3x756, respectively); or (y) pretilachlor (mixtures 3y1 to 3y756,respectively).

Various aspects and embodiments of the present invention will now beillustrated in more detail by way of example. It will be appreciatedthat modification of detail may be made without departing from the scopeof the invention.

For the avoidance of doubt, where a literary reference, patentapplication, or patent, is cited within the text of this application,the entire text of said citation is herein incorporated by reference.

PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA (II) General Experimental

Chiral HPLC was recorded on the columns below with the solvents andgradients stated.

Column:

Regis Whelk 01 (s,s) 4.6×100 mm, 3.5 μm

Chiralpak IC 4.6×100 mm, 3.0 μm

Solvents:

A: iso-Hexane+0.1% glacial Acetic Acid (v/v)

B: Ethanol+0.1% glacial Acetic Acid (v/v)

Gradient:

Time (mins): Flow (mL/min): % A: % B: 0.0 1.0 85 15 1.0 1.0 85 15 7.01.0 50 50 15.0 1.0 40 60

Synthesis Method (I): Racemic Synthesis Route Exemplar compound:′N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide

Salt (I) can be prepared as described in Tetrahedron Lett. 1995, 36,9409.

Step 1 Ethyl(E)-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]prop-2-enoate

In a large microwave vial 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole(3.62 mmol, 1.00 g) was dissolved in acetonitrile (15.2 mL), and ethylacrylate (1.19 mL, 10.9 mmol), triethylamine (0.507 mL, 3.64 mmol),tri-ortho-tolylphosphine (0.362 mmol, 0.110 g) and palladium(II) acetate(0.362 mmol, 0.0813 g) were added, the air space above the stirredorange solution was swept with nitrogen, and the vial sealed and heatedat 110° C. under microwave irradiation for 60 minutes. The reactionmixture was filtered (rinsing through with small portions of EtOAc), andthe combined filtrate and washings were concentrated to remove the bulkof solvent. The residual orange-brown liquid was diluted with water (12mL) and extracted with EtOAc (3×15 mL). The organic extracts werecombined, washed with water (10 mL), passed through a phase separationcartridge then concentrated. Column chromatography (EtOAc/iso-hexanegradient elution) gave ethyl(E)-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]prop-2-enoate as ayellow oil, 0.51 g (57%).

¹H NMR: (400 MHz, CDCl₃): δ=7.58 (d, J=16.1 Hz, 1H), 6.81 (s, 1H), 6.43(d, J=16.1 Hz, 1H), 4.26 (q, J=7.1 Hz, 2H), 4.01 (d, J=0.6 Hz, 3H), 1.33(t, J=7.1 Hz, 3H).

Step 2Ethyl-6-Methyl-8-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-1,4-Dithia-6-Azaspiro[4.4]Nonane-9-Carboxylate

To a suspension of finely divided cesium fluoride (12.7 mmol, 1.93 g) intetrahydrofuran (9.51 mL) stirred at −50° C., under a nitrogenatmosphere, was added a solution of ethyl(E)-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]prop-2-enoate (3.17mmol, 0.787 g) and1,3-dithiolan-2-ylidene-methyl-(trimethylsilylmethyl)ammonium;trifluoromethanesulfonicacid (5.55 mmol, 2.06 g) in tetrahydrofuran (39.51 mL) drop-wise overapprox. 15 minutes, keeping the reaction temperature below −45° C. Theresulting very pale yellow cloudy suspension was allowed to warm slowlyto room temperature and stirring was continued overnight. The reactionmixture was then diluted with DCM and filtered, washing through withfurther portions of DCM. The combined filtrate and washings wereconcentrated, and the crude material purified by column chromatography(EtOAc/cyclohexane gradient elution) givingethyl-6-methyl-8-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-1,4-dithia-6-azaspiro[4.4]nonane-9-carboxylateas a pale yellow oil, 566 mg (45%).

¹H NMR: (400 MHz, CDCl₃): δ=6.45 (s, 1H), 4.31-4.17 (m, 2H), 3.90 (d,J=0.6 Hz, 3H), 3.89-3.79 (m, 2H), 3.35-3.06 (m, 5H), 2.97-2.91 (m, 1H),2.47 (s, 3H), 1.31 (t, J=7.2 Hz, 3H).

Step 31-Methyl-4-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Thioxo-Pyrrolidine-3-CarboxylicAcid

To a solution of ethyl6-methyl-8-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-1,4-dithia-6-azaspiro[4.4]nonane-9-carboxylate(1.43 mmol, 0.566 g) in dioxane (34.3 mL) and water (11.4 mL) was addedLiOH (14.3 mmol, 0.343 g), and the stirred mixture heated to 60° C.under a nitrogen atmosphere for 1 hour. The reaction mixture was thenallowed to cool to around 35° C. then concentrated to remove the bulk ofdioxane. The residual mixture was diluted with water (10 mL), andpartitioned between dilute HCl (5 mL, to pH3) and DCM (20 mL). Thetwo-phase mixture was filtered to remove fine solids then the organicphase was separated. The aqueous was further extracted with DCM (2×15mL), and all organic extracts combined, dried over MgSO₄, filtered andthe filtrate concentrated giving1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxylicacid as a light yellow solid, 399 mg (90%).

¹H NMR: (400 MHz, CDCl₃): δ=6.66 (s, 1H), 4.19-4.03 (m, 4H), 3.93 (d,J=0.5 Hz, 3H), 3.34 (s, 3H).

Step 4N-(2,3-Difluorophenyl)-1-Methyl-4-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Thioxo-Pyrrolidine-3-Carboxamide

To a solution of1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxylicacid (0.340 g, 1.11 mmol) in DCM (8.0 mL) was added 2,3-difluoroaniline(0.112 mL, 1.11 mmol) giving a pale yellow solution. Propylphosphonicanhydride (50 mass %) in ethyl acetate (1.88 mmol, 1.12 mL) was added,followed by the N,N-diisopropylamine (3.32 mmol, 0.578 mL) and thereaction mixture was stirred at room temperature for 1 hour. Thereaction mixture was then quenched by the addition of water (2 mL) withstirring, transferred to a phase separation cartridge and the organicscollected and concentrated. Column chromatography (EtOAc/iso-hexanegradient elution) gaveN-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxamideas a colourless crystalline solid, 264 mg (57%).

¹H NMR: (400 MHz, CDCl₃): δ=10.25 (br s, 1H), 8.01 (tdd, J=1.6, 6.6, 8.3Hz, 1H), 7.04 (ddt, J=2.1, 5.9, 8.3 Hz, 1H), 6.94-6.86 (m, 1H), 6.58 (s,1H), 4.40 (td, J=6.3, 8.6 Hz, 1H), 4.20 (d, J=6.4 Hz, 1H), 4.13 (dd,1H), 4.00 (dd, 1H), 3.93 (d, 3H), 3.33 (s, 3H).

Step 5N-(2,3-Difluorophenyl)-1-Methyl-4-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Oxo-Pyrrolidine-3-Carboxamide

To a solution ofN-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-thioxo-pyrrolidine-3-carboxamide(0.621 mmol, 0.260 g) in acetonitrile (6.21 mL) stirred and cooled toaround 0 to −5° C., in an ice-salt bath, was added 50% hydrogen peroxide(0.746 mL) drop-wise and a white suspension resulted. After 5 minutes45% aq. hydrobromic acid (0.0750 mL, 0.621 mmol) was added drop-wise andafter stirring for 10 minutes the mixture was allowed to warm to roomtemperature. After 3 hours the reaction mixture was re-cooled to 5° C.,and quenched with sodium thiosulfate solution (˜10 mL). The mixture wasdiluted with EtOAc (15 mL) and water (10 mL), and the organic phaseseparated. The aqueous was further extracted with EtOAc (2×10 mL), thenthe organic extracts were combined, run through a phase separationcartridge then concentrated giving a colourless gum. Columnchromatography (EtOAc/iso-hexane gradient elution) gaveN-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamideas a white crystalline solid, 210 mg (84%).

¹H NMR: (400 MHz, CDCl₃): δ=10.15 (br s, 1H), 8.04 (dd, J=6.6, 8.3 Hz,1H), 7.06-6.99 (m, 1H), 6.89 (br dd, J=1.1, 8.6 Hz, 1H), 6.69 (s, 1H),4.09 (q, 1H), 3.94 (s, 3H), 3.78 (d, J=9.5 Hz, 1H), 3.76-3.65 (m, 2H),2.98 (d, 3H).

The racemicN-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamidecould be separated to afford the enantiomers(3S,4R)—N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3carboxamide and(3R,4S)—N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamideusing a Chiralpak IA, 10×250 mm, 5 μm column with sc-CO₂ (solvent A)B=Isopropanol (solvent B) as solvents under isocratic conditions: 85%solvent A:15% solvent B at 15 mL/min.

Synthesis Method (II): Asymmetric Synthesis Route Exemplar compound:′(3S,4R)—N-(2,3-difluorophenyl)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxamide

The Nickel catalyst used in step 3, which catalyses the asymmetricmalonate addition to the nitro olefin, can be prepared as in J. Am.Chem. Soc. 2005, 127, 9958-9959.

Step 1 3-Iodo-1-Methyl-5-(Trifluoromethyl)Pyrazole

The compound 1-methyl-5-(trifluoromethyl)pyrazol-3-amine (5.00 g, 30.3mmol) was stirred in 9M sulfuric acid (818 mmol, 91 mL) in a 500 mLbeaker, using an overhead stirrer at 0° C. (ice bath) until a homogenousmixture resulted. Sodium nitrite (60.6 mmol, 4.18 g), in 10 mL of water,was then added dropwise over 5 minutes, resulting in a colourlesssolution and the reaction was stirred at 0° C. for a further 20 minutes.Potassium iodide (75.7 mmol, 12.6 g), in 20 mL of water, was addeddropwise to the reaction and the mixture was then stirred for a further4 hours. The reaction was quenched with saturated sodium thiosulfateuntil the mixture became clear. The mixture was then diluted withdichloromethane and the phases were separated. The aqueous was furtherextracted with dichloromethane and the combined organic extracts werewashed with water, dried (MgSO4), filtered and concentrated under vacuumto afford a pale yellow oil. The crude product was purified by columnchromatography (EtOAc/hexanes gradient elution) to afford3-iodo-1-methyl-5-(trifluoromethyl)pyrazole as a colourless oil, 3.9 g,(47%).

¹H NMR (400 MHz, CDCl₃)=6.76 (s, 1H) 4.01 (d, J=0.61 Hz, 3H).

Step 2 1-Methyl-3-[(E)-2-Nitrovinyl]-5-(Trifluoromethyl)Pyrazole

Isopropylmagnesium chloride-Lithium chloride in THF (23.55 mmol, 1.3mol/L) was added dropwise to 3-iodo-1-methyl-5-(trifluoromethyl)pyrazole(5.0 g, 18.12 mmol) in THF (90 mL) at −20° C. and the mixture wasstirred for 2 hours. 1-Dimethylamino-2-nitroethylene (27.17 mmol, 3.321g) was added and the reaction was slowly warmed to RT over 1 hour. Thereaction mixture was then carefully quenched with 2 M HCl, and extractedwith ethyl acetate. The organic extracts were washed with brine, dried(MgSO4), filtered, concentrated and purified by chromatography(EtOAc/cyclohexane gradient elution) to afford1-methyl-3-[(E)-2-nitrovinyl]-5-(trifluoromethyl)pyrazole (74.6%) as ayellow oil, 2.99 g (74.6%).

¹H NMR (400 MHz, CDCl₃)=7.89 (d, J=13.7 Hz, 1H), 7.63 (d, J=13.7 Hz,1H), 6.88 (s, 1H), 4.05 (d, J=0.6 Hz, 3H).

Step 3 Diethyl 2-[(1S)-1-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Nitro-Ethyl]Propanedioate

To a solution of1-methyl-3-[(E)-2-nitrovinyl]-5-(trifluoromethyl)pyrazole (0.650 g, 2.94mmol) in toluene (19.5 mL) was added diethyl malonate (0.676 mL, 4.41mmol) followed byNickel(II)Bis[(1R,2R)—N1,N2-bis(phenylmethyl)-1,2-cyclohexanediamine-N1,N2]dibromide(0.0588 mmol, 0.0472 g), and the mixture was stirred at ambienttemperature for 20 hours.

The reaction mixture was washed with water (2×10 mL) and the organicphase separated, concentrated and purified by chromatography(EtOAc/cyclohexane gradient elution) to afford diethyl2-[(1S)-1-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-nitro-ethyl]propanedioateas pale yellow oil, 1.07 g (95%).

¹H NMR (400 MHz, CDCl₃)=6.53 (s, 1H), 5.01 (dd, 1H), 4.88 (dd, J=4.3,13.9 Hz, 1H), 4.35 (ddd, J=4.4, 7.7, 9.0 Hz, 1H), 4.22 (q, 2H), 4.16 (q,J=7.1 Hz, 2H), 3.90 (s, 3H), 3.89 (d, 1H), 1.26 (t, 3H), 1.20 (t, J=7.2Hz, 3H).

Step 4 Ethyl(3R,4R)-4-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Oxo-Pyrrolidine-3-Carboxylate

To a solution of diethyl2-[(1R)-1-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-nitro-ethyl]propanedioate(1.07 g, 2.81 mmol) in ethanol (42.1 mL) cooled to 0-5° C. (ice bath)under nitrogen, was added dichloronickel hexahydrate (2.95 mmol, 0.700g). Sodium borohydride (8.42 mmol, 0.325 g) was then added portionwiseto the pale greenish-blue solution. After 30 minutes the cooling wasremoved and the reaction mixture allowed to warm to ambient temperature.After stirring for 5 hours, at ambient temperature, the reaction mixturewas cooled to 5-10° C., in an ice-water bath, and slowly quenched withammonium chloride solution, and the mixture stirred for a further 20minutes. The mixture was then diluted with EtOAc (20 mL), and filteredthrough a bed of celite, washing through with portions of water andEtOAc. The collected two-phase mixture was concentrated to remove thebulk of solvent and the residue transferred to a separating funnel,diluted with EtOAc (20 mL) and the organic phase separated. The aqueousphase was further extracted with EtOAc (2×25 mL) and all organicextracts combined, passed through a phase separation concentrated andpurified by chromatography (EtOAc/hexanes gradient elution) to afford apale yellow oil, 0.61 g (77%) which crystallised on standing. 1H NMR(400 MHz, CDCl₃) b=6.91 (br s, 1H), 6.47 (s, 1H), 4.28 (q, J=7.2 Hz,2H), 4.14 (q, 1H), 3.94 (d, 3H), 3.80 (dt, J=1.0, 9.0 Hz, 1H), 3.63 (d,J=9.3 Hz, 1H), 3.52 (dd, J=8.2, 9.5 Hz, 1H), 1.32 (t, J=7.2 Hz, 3H).

Step 5(3R,4R)-4-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Oxo-Pyrrolidine-3-CarboxylicAcid

To a solution of ethyl(3R,4R)-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylate(0.61 g, 2.0 mmol) in ethanol (6.0 mL) and water (2.0 mL) at 0° C. (icebath) was added 2M sodium hydroxide (3 mL, 6.0 mmol). The reactionmixture was stirred at 0° C. for 30 minutes and then diluted with water(15 mL) and extracted with EtOAc (25 mL). The organic extracts werewashed with water (10 mL), and the aqueous extracts combined andacidified to pH 2 with dilute HCl. The acidified aqueous extracts werethen re-extracted with EtOAc (3×20 mL) and these organic extracts wererun through a phase separation cartridge and concentrated affording apale yellow oil, 0.54 g (quantitative) which crystallised on standing.

¹H NMR (400 MHz, CDCl3) □=6.59 (s, 1H), 4.09 (q, 1H), 3.94 (s, 3H),3.85-3.77 (m, 1H), 3.72 (d, J=10.0 Hz, 1H), 3.66-3.58 (m, 1H).

Step 6(3R,4R)-1-Methyl-4-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Oxo-Pyrrolidine-3-CarboxylicAcid

To a stirred solution of(3R,4R)-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylicacid (0.57 g, 2.1 mmol, 0.57 g) in tetrahydrofuran (16 mL), at roomtemperature, under a nitrogen atmosphere was added potassium tertiarybutoxide (1.0M in THF) (4.5 mL, 4.5 mmol) giving a pale yellow finesuspension. To this suspension was added iodomethane (0.19 mL, 3.1mmol), and stirring at room temp was continued for 20 h. The stirredreaction mixture was acidified to pH2 with dilute HCl and the mixturewas diluted with water (10 mL) and extracted with EtOAc (3×30 mL). Thecombined organic extracts were washed with brine (15 mL), dried overmagnesium sulfate, filtered and the filtrate concentrated giving atransparent amber gum, 0.63 g ((quantitative).

¹H NMR: (400 MHz, CDCl3) b=6.68 (s, 1H), 3.97 (q, 1H), 3.94 (s, 3H),3.76-3.68 (m, 3H), 2.99 (s, 3H).

Step 7(3S,4R)—N-(2,3-Difluorophenyl)-1-Methyl-4-[1-Methyl-5-(Trifluoromethyl)Pyrazol-3-Yl]-2-Oxo-Pyrrolidine-3-Carboxamide

To a solution of(3R,4R)-1-methyl-4-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-oxo-pyrrolidine-3-carboxylicacid (0.61 g, 2.1 mmol) in dichloromethane (15 mL) was added2,3-difluoroaniline (0.21 mL, 2.1 mmol). Propylphosphonic anhydride (50mass %) in ethyl acetate (2.3 g, 3.6 mmol, 2.1 mL) was then added, andthe reaction mixture was then immersed in a room temp water bath.N,N-Diisopropylethylamine (1.1 mL, 6.3 mmol) was added drop-wise, andthe reaction was stirred at room temperature for 2.5 hour. The reactionmixture was quenched by the addition of water (15 mL) and transferred toa phase sep cartridge. The aqueous was further extracted with DCM (2×10mL) and the combined organic extracts were concentrated and purified bychromatography (EtOAc/hexanes gradient elution) to afford a pink oil.Trituration with iso-hexane afforded a pale pink solid 398 mg (47%). 1HNMR: (400 MHz, CDCl₃) b=10.16 (br s, 1H), 8.08-8.01 (m, 1H), 7.02 (ddt,J=2.1, 5.9, 8.3 Hz, 1H), 6.93-6.84 (m, 1H), 6.69 (s, 1H), 4.09 (q, 1H),3.94 (s, 3H), 3.78 (d, J=9.5 Hz, 1H), 3.76-3.65 (m, 2H), 2.98 (s, 3H).

Chiral HPLC analysis, by the methods stated above, confirmed anenantiomeric ratio of 97:3.

Further compounds of formula (II) were synthesized in an analogousmanner using the above described two synthetic routes. These are shownin Tables 3 and 4 below.

TABLE 3 Compounds of formula (II) prepared using synthesis method (I)NMR data corresponds to that for the repective racemates Compound No.Structure 1HNMR (CDCl₃) 2.1

δ = 10.15 (br s, 1H), 8.04 (tdd, J = 1.6, 6.6, 8.3 Hz, 1H), 7.02 (ddt, J= 2.1, 5.9, 8.3 Hz, 1H), 6.93-6.85 (m, 1H), 6.69 (s, 1H), 4.09 (q, 1H),3.94 (s, 3H), 3.81-3.65 (m, 3H), 2.98 (d, 3H) 2.2

δ = 10.04 (br s, 1H), 8.31- 8.25 (m, 1H), 7.13-7.00 (m, 3H), 6.69 (s,1H), 4.11 (q, 1H), 3.94 (s, 3H), 3.80-3.65 (m, 3H), 2.98 (d, 3H) 2.3

δ = 9.98 (br s, 1H), 8.22 (dt, J = 6.0, 8.9 Hz, 1H), 6.90-6.80 (m, 2H),6.69 (s, 1H), 4.09 (q, 1H), 3.94 (d, 3H), 3.80-3.65 (m, 3H), 2.97 (d, J= 0.7 Hz, 3H) 2.4

δ = 10.40 (s, 1H), 8.17 (td, J = 1.5, 8.5 Hz, 1H), 7.26-7.19 (m, 1H),6.92 (ddd, J = 1.4, 8.4, 9.7 Hz, 1H), 6.69 (s, 1H), 4.07 (q, J = 9.0 Hz,1H), 3.94 (s, 3H), 3.77 (d, 1H), 3.74- 3.64 (m, 2H), 2.98 (s, 3H) 2.5

δ = 10.16 (br s, 1H), 7.99 (d, J = 8.3 Hz, 1H), 7.46 (dt, J = 6.0, 8.4Hz, 1H), 7.00-6.92 (m, 1H), 6.68 (s, 1H), 4.09 (q, J = 8.9 Hz, 1H), 3.94(s, 3H), 3.79-3.66 (m, 3H), 2.98 (d, 3H) 2.6

δ = 10.21 (s, 1H), 8.13 (td, J = 1.3, 8.4 Hz, 1H), 6.96 (dt, J = 5.7,8.3 Hz, 1H), 6.81 (ddd, J = 1.5, 8.4, 11.1 Hz, 1H), 6.68 (s, 1H), 4.13(q, J = 9.0 Hz, 1H), 4.03 (d, J = 1.7 Hz, 3H), 3.94 (d, 3H), 3.78-3.63(m, 3H), 2.97 (d, J = 0.7 Hz, 3H) 2.7

δ = 10.08 (br s, 1H), 8.01- 7.94 (m, 1H), 6.92 (ddt, J = 2.4, 7.7, 9.7Hz, 1H), 6.68 (s, 1H), 4.07 (q, 1H), 3.94 (s, 3H), 3.77 (d, 1H),3.75-3.65 (m, 2H), 2.98 (d, 3H) 2.8

δ = 10.17 (br s, 1H), 8.83- 8.76 (m, 1H), 6.80 (dd, J = 2.9, 8.6 Hz,1H), 6.67 (s, 1H), 4.07 (q, J = 8.9 Hz, 1H), 3.95 (d, 3H), 3.83-3.65 (m,3H), 2.98 (d, 3H) 2.9

δ = 10.04 (s, 1H), 8.01 (dd, J = 1.8, 7.9 Hz, 1H), 7.75 (q, J = 8.1 Hz,1H), 6.65 (s, 1H), 6.64 (dd, 1H), 4.12 (q, J = 9.0 Hz, 1H), 3.94 (s,3H), 3.77- 3.61 (m, 3H), 2.96 (s, 3H) 2.10

δ = 10.29 (s, 1H), 8.17 (td, J = 1.3, 8.4 Hz, 1H), 7.17 (dt, J = 5.9,8.5 Hz, 1H), 6.89 (ddd, J = 1.3, 8.5, 10.0 Hz, 1H), 6.68 (s, 1H), 6.67(t[large F coupling], 1H), 4.09 (q, J = 9.0 Hz, 1H), 3.94 (s, 3H), 3.78(d, J = 9.5 Hz, 1H), 3.75-3.63 (m, 2H), 2.98 (m, 3H) 2.11

δ = 9.73 (s, 1H), 8.05 (d, 1H), 7.34-7.27 (m, 1H), 7.22- 7.16 (m, 1H),7.10-7.05 (m, 1H), 6.72 (s, 1H), 4.17-4.07 (m, 1H), 3.94 (s, 3H), 3.77-3.66 (m, 3H), 2.97 (d, 3H), 2.77-2.65 (m, 2H), 1.27 (t, 3H) 2.12

δ = 9.75 (br s, 1H), 8.11 (dd, J = 5.1, 9.0 Hz, 1H), 7.21 (dd, J = 2.9,9.2 Hz, 1H), 7.13-7.06 (m, 1H), 6.67 (s, 1H), 4.13 (q, J = 8.9 Hz, 1H),3.94 (s, 3H), 3.76-3.64 (m, 3H), 2.97 (s, 3H), 1.98 (t, 3H) 2.43

δ = 10.14 (s, 1H), 8.09- 7.97 (m, 1H), 7.08-6.97 (m, 1H), 6.92-6.82 (m,1H), 6.27 (s, 1H), 4.10- 3.97 (m, 1H), 3.88-3.75 (m, 1H), 3.80 (s, 3H),3.74-3.60 (m, 2H), 2.95 (s, 3H). 2.45

δ = 9.96 (brs, 1H), 8.28- 8.18 (m, 1H), 6.91- 6.77 (m, 2H), 6.27 (s,1H), 4.05 (q, J = 9.0 Hz, 1H), 3.83-3.60 (m, 3H), 3.79 (s, 3H), 2.96 (s,3H) 2.49

δ = 10.06 (s, 1H), 8.03- 7.93 (m, 1H), 6.98-6.85 (m, 1H), 6.27 (s, 1H),4.03 (q, 1H), 3.83-3.60 (m, 3H), 3.80 (s, 3H), 2.97 (s, 3H).

TABLE 4 Compounds of formula (II) prepared using synthesis method (II)NMR data corresponds to that for the single enantiomer as shown CompoundNo. Structure 1HNMR (CDCl₃) 2.1

δ = 10.15 (br s, 1H), 8.04 (dd, J = 6.6, 8.3 Hz, 1H), 7.06-6.99 (m, 1H),6.89 (br dd, J = 1.1, 8.6 Hz, 1H), 6.69 (s, 1H), 4.09 (q, 1H), 3.94 (s,3H), 3.78 (d, J = 9.5 Hz, 1H), 3.76-3.65 (m, 2H), 2.98 (d, 3H) 2.15

δ = 10.05 (br s, 1H), 8.04- 7.97 (m, 1H), 7.46 (s, 1H), 7.01 (ddt, J =2.1, 5.9, 8.3 Hz, 1H), 6.93-6.84 (m, 1H), 4.21 (q, J = 8.8 Hz, 1H), 4.00(s, 3H), 3.75 (t, J = 9.5 Hz, 1H), 3.64 (d, J = 9.4 Hz, 1H), 3.27 (dd, J= 8.1, 9.9 Hz, 1H), 2.97 (s, 3H)

Biological Examples

Herbicidal Efficacy of Compounds of Formula (II)

Seeds of a variety of test species [Ipomoea hederacea (IPOHE); Zea mays(ZEAMX); Echinochloa crus-galli (ECHCG); Setaria faberi (SETFA);Abutilon theophrasti (ABUTH); Amaranthus retroflexus (AMARE)] were sownin standard sterilised soil in pots. After cultivation for one day(pre-emergence) or after 8 days cultivation (post-emergence) undercontrolled conditions in a glasshouse (at 24/16° C., day/night; 14 hourslight; 65% humidity), the plants were sprayed with an aqueous spraysolution derived from the formulation of the technical active ingredientin acetone/water (50:50) solution containing 0.5% Tween 20(polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5), subsequentlydiluted in water, and sprayed to give the stated application rate.

The test plants were then grown under controlled conditions in aglasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity) andwatered twice daily.

After 13 days for pre and post-emergence, the test was evaluatedvisually for percentage phytotoxicity to the plant (where 100=totaldamage to plant; 0=no damage to plant). Results are shown in Tables B1and B2.

TABLE B1 Application post-emergence Compound Rate Number (g/ha) AMAREABUTH SETFA ECHCG ZEAMX IPOHE 2.1 250 20 0 90 90 80 0 2.3 250 10 60 7070 60 10 2.2 250 0 0 90 90 50 0 2.4 250 0 0 70 70 0 0 2.7 250 50 0 80 8080 0 2.6 250 0 0 70 70 80 50 2.5 250 30 0 80 80 10 0 2.11 250 20 0 80 800 0 2.8 250 0 0 80 80 80 30 2.10 250 0 0 80 80 80 30 2.9 250 0 0 80 8040 50 2.12 250 0 0 90 90 80 50 2.15 250 0 0 80 80 30 40

TABLE B2 Application pre-emergence Compound Rate Number (g/ha) AMAREABUTH SETFA ECHCG ZEAMX IPOHE 2.1 250 70 10 90 100 90 30 2.3 250 50 7090 90 60 10 2.2 250 20 0 90 90 20 0 2.4 250 0 0 90 90 30 50 2.7 250 2010 90 100 90 20 2.6 250 0 0 90 90 80 20 2.5 250 0 0 90 90 20 10 2.11 25070 0 90 90 20 0 2.8 250 20 0 90 90 40 0 2.10 250 0 0 90 90 40 20 2.9 2500 0 90 100 80 40 2.12 250 0 0 90 90 90 70 2.15 250 0 40 100 100 40 20

The invention claimed is:
 1. A composition, comprising: (A) a compoundof formula (I):

wherein R¹ is methyl or methoxy, R² is hydrogen, methyl or ethoxy and Ais a substituted heteroaryl group and wherein said compound is selectedfrom the group consisting of

or an N-oxide or salt form thereof; and (B) one or more compounds offormula (II):

wherein R^(B1) is H, methyl, or methoxy; X is O or S; Q¹ is adi-substituted pyrazole, substituted on one ring nitrogen by R^(B2) andon an adjacent ring carbon by R^(B3), wherein R^(B2) is C₁-C₃ alkyl andR^(B3) is independently bromo, iodo, C₁-C₃haloalkoxy, C₁-C₃alkoxy,C₁-C₃haloalkyl, or C₁-C₃alkyl; or R^(B2) is C₁-C₃ alkyl and R^(B3) isC₁-C₃fluoroalkyl or C₁-C₃alkyl, and R^(B2) and R^(B3) together with theatoms to which they are joined and Q¹ form an eight or nine-memberedfused heterocyclic bicyclic ring system; Q² is a phenyl, pyridinyl, orthienyl ring system, optionally substituted by 1, 2, or 3 R^(B5)substituents; and each R^(B5) is independently halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, cyano, nitro,C₁-C₆alkylthio, C₁-C₆alkylsulphinyl, or C₁-C₆alkylsulphonyl; or anN-oxide, or a salt form thereof.
 2. The composition of claim 1, R^(B1)is H or methyl.
 3. The composition of claim 1, wherein X is O.
 4. Thecomposition of claim 1, wherein Q² is selected from the group consistingof Q²-1, Q²-2, Q²-3, Q²-4, Q²-5, and Q²-6,

wherein n is 0, 1, 2, or 3, R^(B5) is as defined in claim 1, and thejagged line represents the point of attachment to the rest of themolecule.
 5. The composition of claim 1, wherein each R^(B5) isindependently halogen, C₁-C₄alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, orC₁-C₃haloalkoxy.
 6. The composition of claim 1, wherein Q¹ is selectedfrom the group consisting of Q¹-2a and Q¹-2b

and R^(B3SN) is independently selected from bromo, iodo,C₁-C₃fluoroalkyl, C₁-C₃haloalkoxy, C₁-C₃alkoxy, and C₁-C₃alkyl, and thejagged line denotes the point of attachment to the rest of the molecule.7. The composition of claim 1, wherein R^(B2) is selected from the groupconsisting of methyl, ethyl, and n-propyl.
 8. The composition of claim1, wherein Q¹ is a di-substituted pyrazole ring system, and R^(B2) andR^(B3) together with the atoms to which they are joined and Q¹ form aneight or nine-membered fused hetero-bicyclic ring system.
 9. Thecomposition of claim 1, wherein the eight or nine-membered fusedhetero-bicyclic ring system is selected from the group consisting ofQ¹-F1 to Q¹-F12 as shown below:

wherein the jagged line denotes the point of attachment to the rest ofthe molecule.
 10. The composition of claim 1, further comprising a thirdcomponent (C), selected from the group consisting of mesotrione,bicyclopyrone, atrazine, S-metholachlor, terbuthylazine, dimethaclor,flufenacet, glyphosate, isoxaflutole, nicosulfuron, ametryn, hexazinone,paraquat, diquat, pyridate, acetochlor, dimethenamid-P, alachlor,pethoxamid, pyroxosulfone, trifloxysulfuron sodium, flazasulfuron,prosulfocarb, metolachlor, and pretilachlor.
 11. The composition ofclaim 1, further comprising one or more safeners selected from the groupconsisting of AD 67, benoxacor, cloquintocet-mexyl, cyometrinil,cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole-ethyl,fenclorim, flurazole, fluxofenim, furilazole, furilazome,isoxadifen-ethyl, mefenpyr-diethyl, mephenate, oxabetrinil, naphthalicanhydride, TI-35, N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide,andN-(2-methoxybenzoyl)-4-Rmethylaminocarbonyl)aminoThenzenesulfonamide.